CN1257511A - Olefin copolymers from bridged bis(arylamido) group 4 catalyst compounds - Google Patents

Olefin copolymers from bridged bis(arylamido) group 4 catalyst compounds Download PDF

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CN1257511A
CN1257511A CN98802644A CN98802644A CN1257511A CN 1257511 A CN1257511 A CN 1257511A CN 98802644 A CN98802644 A CN 98802644A CN 98802644 A CN98802644 A CN 98802644A CN 1257511 A CN1257511 A CN 1257511A
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olefin
monomer
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CN100389131C (en
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T·D·沙佛
K·R·斯奎瑞
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ExxonMobil Chemical Patents Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/08—Butenes
    • C08F10/10—Isobutene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/14—Monomers containing five or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/06—Hydrocarbons
    • C08F12/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14—Monomers containing five or more carbon atoms

Abstract

A process for preparing substantially random olefin copolymers containing geminally disubstituted olefin monomers is described. The geminally disubstituted olefin monomers can be represented by the generic formula R1 = R2(R3)(R4), where R1 is CH2, R2 is C, and R3 and R4 are, independently, essentially linear hydrocarbyl groups having from 1 to 30 carbon atoms, or more, and containing one carbon atom bound directly to R2. The copolymers can be prepared by contacting at least one geminally disubstituted olefin monomer and one or more comonomers selected from the group consisting of ethylene and C3-C20 alpha -olefins, optionally with one or more other coordination polymerizable monomers, with an active coordination catalyst system comprising a bridged bis(arylamido) Group 4 catalyst component.

Description

Olefin copolymer by the catalyst compound preparation of bridging two (arylamino) the 4th family
Field of the present invention
The present invention relates to contain at least a alpha-olefin copolymer and their polymerization process of preparation together with disubstituted olefin monomer.The present invention more specifically relates in the presence of two (arylamino) the 4th family's catalyst compound of bridging the copolymerization alpha-olefin and together with the method for disubstituted olefin monomer and the polymkeric substance that is prepared by this method.
Background of the present invention
Insertion or polycoordination are the polymkeric substance of known preparation ethene, alpha-olefin, non-conjugated diene hydrocarbon and cycloolefin and the chemical reaction method of multipolymer.The polycoordination of carrying out with the group-4 metal ocene catalyst system is known especially at present.Traditional Z iegler monomer, for example easily polymerization in the presence of having as the 4th group 4 transition metal of at least one η-5 bonding cyclopentadienyl ligands of part and two monovalent anion parts of ethene and alpha-olefin (as propylene, 1-butylene, 1-hexene and 1-octene), wherein monovalent ligands can be captured the activating catalytic immunomodulator compounds that formation thus can be carried out the alkene insertion polymerization by cocatalyst compound.
Thought and can not carry out polymerization by insertion or coordination mechanism basically together with disubstituted olefin monomer (as iso-butylene).At polymer science and engineering encyclopedia, the 8th volume, p.175 in " insertion polymerization " chapter of (Wiley Interscience, 1988), point out " ... 1,1-two substituted alpha-alkenes can not carry out homopolymerization or carry out copolymerization with other monoolefine." the dibasic alpha-olefin of this class generally carries out positively charged ion or carbon cation polymerization and copolymerization by the lewis acid catalyst system that forms carbocation with known initiation.Yet, since ethene be not easy by the polymerization of positively charged ion technology (referring to Kennedy, J.P., carbon cation polymerization alkene: an important invention, p.53 etc., John Wiley ﹠amp; Sons, 1975), the multipolymer of ethene and two substituted alpha-alkenes is unknown on substantially.
Although there is this prejudice in the prior art, but provided the example of some ethene-isobutylene copolymers.The embodiment E of W0 95/29940 has been described and ethene/iso-butylene copolymerization of using two (cyclopentadienyl) dimethyl hafniums and two (pentamethyl-cyclopentadienyl) zirconium dimethyls (all using the activation of trityl group four (perfluorophenyl) boron) equal polyisobutene and ethene to carry out simultaneously down at-20 ℃.Ethene-isobutylene copolymers the amount that generates is lower than the 1.3wt% of total polymer product." the alkene isotaxy polymerization of carrying out with the homogeneous phase Zr catalyst " used by the copolymerization of methylaluminoxane activatory ethylenebis (indenyl) zirconium dichloride and be disclosed in to 2-methacrylic (iso-butylene) and ethene under 30 ℃ and 50 ℃, people such as W.Kaminsky, transition metal and organometallic compound as olefin polymerization catalysis, p291, in 296 (Springer-Verlag, 1988).The iso-butylene that report is introduced is lower than 2.8mol%, and an only example provides 1.35mol%.
In the alpha-olefine polymerizing field, also know two (amino) the 4th family's catalyst compound of non-metallocene.US5,318,935 have described group-4 metal bridging and the non-bridged two amino transition metal catalyst compound that can carry out the alpha-olefin insertion polymerization.Embodiment has provided the alpha-olefin copolymer and the homopolymer of ethene, propylene, 1-butylene and 1-hexene.US 4,774, and 301 have described general molecular formula ZrXR 3The Zr catalyst compound, wherein the R group can comprise one or more-NR ' 2Group, R ' are the alkyl or aryl of 12 carbon atoms at the most.Yet, only described the polymerizing power and the Qi Gao syndiotactic polymer of vi-ny l aromatic monomers, and only provided the example for preparing syndiotactic polystyrene with four n-propoxyzirconium.Two (arylamino) the 4th compounds of group of bridging that recommendation is used for " single-point " olefinic polymerization are described in organo-metallic journal 1995,14 by people such as D.H.McConville, among the 5478-5480.Having provided synthetic method and compound characterizes.People such as D.H.McConville, macromole 1996,29, another job description of 5241-5243 report be used for two (arylamino) the 4th compounds of group of bridging of polymerization 1-hexene, this compound provides deactivated catalyst by the activation of Lewis acid promotor.These documents are introduced as reference according to patent practice.
In sum, need to prepare the polyolefinic other method that is mixed with together with disubstituted olefin especially.Comprise alpha-olefin and provide the novel composition that can be used for a lot of fields together with the copolymer compositions of disubstituted olefin and non-essential other polymerizable ethylenically unsaturated monomer.Also play the effect of using the intrinsic additional raw material in the petroleum refining process economically, wherein fractionation can be produced the mixed flow of 1-butylene and iso-butylene.
The present invention is open
Therefore, the present invention relates to prepare the polymerization process that contains at least a alpha-olefin copolymer together with disubstituted olefin monomer, comprise alpha-olefin is contacted with two (arylamino) the 4th family's catalyst compound of bridging under the insertion polymerization condition together with disubstituted olefin monomer with at least a.The present invention includes and contain one or more C 3-C 20Poly-alpha-olefin segment and copolymerization are together with the random basically olefin copolymer of disubstituted olefin monomer.Description of the present invention and embodiment
Olefin copolymer of the present invention is generally and comprises one or more alpha-olefins and together with disubstituted olefin monomer, but and the monomeric random basically olefin copolymer of non-essential one or more other polycoordinations.The term " random basically " that is used to describe multipolymer among the present invention be meant multipolymer of the present invention comprise by the random interval of (B) olefin polymer sequence contain ethene or alpha-olefin and together with (A) sequence of the alternating copolymerization monomer structure of disubstituted olefin monomer, it is characterized in that each introducing together with disubstituted olefin monomer between mix at least a ethene or 'alpha '-olefin monomers.Ethylene copolymer can be expressed as comprise random introducing-(E-G) a-and-(E) bThe multipolymer of-sequence, wherein E represents the (CH of derived from ethylene 2-CH 2-) unit, G represents derived from (the CH together with disubstituted monomer 2-C (R 3) (R 4)-) unit, wherein R 3And R 4The alkyl that further defines below being essentially.A and b value are respectively each unitary molar fraction, the wherein a+b=1 that constitutes this multipolymer.Therefore " a " can be from being lower than 0.03 to 1.00, and " b " can from 0.00 to 0.97 and bigger.For example when iso-butylene in reaction process with respect to ethene with height introducing amount (near the 50/50mol% ratio) as together with disubstituted monomer the time, " b " value near 0 and polymkeric substance near the statistics alternating copolymer of ethene and iso-butylene.
Propylene or more high alpha-olefin can be with together with the disubstituted monomer copolymerization, the random basically alpha-olefin of preparation/thus in addition, have been found together with disubstituted monomer multipolymer, for example propylene-isobutylene copolymers according to the inventive method.This analog copolymer has the feature of above-described ethylene copolymer, but propylene wherein or more high alpha-olefin replaced ethene.These multipolymers can be expressed as comprise random introducing-(P-G) a-and-(P) bThe multipolymer of-sequence, wherein P represents the branching or the straight chain unit of derived from propylene or high alpha-olefin, G represents derived from (the CH together with disubstituted monomer 2-C (R 3) (R 4)-) unit, wherein R 3And R 4The alkyl that further defines below being essentially.Early stage work in 030 (application on May 21st, 1996), these multipolymers and comprise one or more C are described and common pending application U.S.Ser.No.08/651 with respect to background technology 3-C 20Poly-alpha-olefin segment and copolymerization are astonishing especially together with the olefin copolymer of disubstituted olefin monomer.This OJT ethene is the essential comonomer together with disubstituted olefin monomer, obviously plays the effect that promotes to introduce together with the required insertion mechanism of disubstituted olefin monomer.These instructions have illustrated that the inventive method improves the ability that can use alkene except that ethene.
Therefore use catalyst compound of the present invention, ethene is overcome as the necessity of restricted processing condition, and can prepare and comprise the more multipolymer of higher alkene.These polymkeric substance can be a kind of non-ethylene alpha olefin and one or more multipolymers together with disubstituted olefin monomer, or two or more different non-ethylene alpha olefins with together with the polymkeric substance of disubstituted olefin monomer.By discovering that the present invention carries out, C 3-C 20The alpha-olefinic polymer segment is unbodied, and promptly prochiral olefin is not the stereospecific orientation in the polymer segment with catalyst compound preparation of the present invention.
As mentioned above, but the random basically multipolymer of the present invention also can comprise one or more coordinations or insert comonomer, wherein together with disubstituted olefin monomer by random introducing.For example, but gained ter-polymers, quadripolymer etc. are representative with the ethene, alpha-olefin and/or other polycoordination monomer segment that comprise random introducing with polymkeric substance together with disubstituted olefin monomer in one embodiment.Term used herein " random introducing " is meant that no homopolymerization together with the disubstituted olefin monomer segment, does not promptly exist in any polymer segment, or does not exist adjacent together with disubstituted olefin monomer at least basically.
Introduce in the multipolymer of the present invention and can change according to the method condition together with disubstituted olefin monomer, particularly used comonomer concentration not only can reach the low amount of instructing in the prior art in the copolymerization, for example from 0 (not having comonomer) to 1.3 or 2.8mol%, and can surpass easily and should lowly measure, for example 3.0 to about 50mol%.Amount of comonomers 8 to 44mol% is exemplary in this application and is representational.
According to introduce together with disubstituted olefin monomer amount and the comonomer chosen, the present invention can prepare from crystallization (ethylene copolymer) to elastic polymkeric substance.Used term " elastomerics " or " elastic " are meant in the prior art confirmedly among the application, and promptly multipolymer is gone up substantially to unbodied, and they do not contain the crystallization segment of obvious amount, for example are no more than 15wt%.Generality description for elasticity ethene-alpha-olefin copolymer degree of crystallinity is recorded in common pending application US08/545, and in 973 (applyings date 9/25/95), its disclosed content is introduced as reference according to patent practice here.Conspicuous as those skilled in the art, destroy any polyethylene crystalline structure and also can realize by other polycoordination monomer of introducing available polymerizing catalyst copolymerization of the present invention in addition.
The amount of 'alpha '-olefin monomers (with ethene or replacement ethene) in multipolymer of the present invention can be about 50mol% to 99.9mol%.Therefore, the traditional ethylene-propylene rubber polymer that has propylene content 8 to 50mol% usually can be used together with disubstituted monomer, and for example iso-butylene replaces propylene production.But other alpha-olefin and polycoordination monomer can be introduced on a small quantity, are usually less than 20mol%.In addition, can prepare and comprise that one or more are together with disubstituted olefin monomer and C only 3-C 20Alpha-olefin, but a small amount of other polycoordination polymer of monomers added.As long as exist above-mentioned molar weight together with disubstituted monomer, comprise that their polymkeric substance just can have one or more C of any residual content 3-C 20Alpha-olefin, for example alpha-olefin of 50-90mol%.
Multipolymer of the present invention will have M nAbout 300 to 300,000 dalton of (number-average molecular weight) value, about 700 to 200,000 dalton more generally are lower than 100,000 dalton usually.Use for lower molecular weight, as be used for those multipolymers of lubricated and fuel oil composition, M nPreferred 300 to 15,000, more preferably less than or equal 10,000.
Be used for any monomer that consists essentially of together with disubstituted olefin of the present invention with following general formula:
R 1=R 2(R 3) (R 4) R wherein 1Be CH 2, R 2Be C, R 3And R 4Be essentially independently and contain at least one and R 2The alkyl of the carbon atom of bonding.R 3And R 4Be preferably and have 1 to 100 carbon atom, preferred 30 or still less straight chain, branching or the ring-type of carbon atom replace or unsubstituting hydrocarbyl R 3And R 4Optionally be joined together to form ring texture.Therefore term comprises two kinds of monomers together with disubstituted olefin, as iso-butylene and the big monomer with above-mentioned exemplary configuration.Although R 3And R 4Be essentially alkyl; but also can comprise non-alkyl atom (as O, S, N, P, Si, halogen atom etc.); wherein these atoms are enough away from two keys, so that do not disturb the polycoordination reaction of using catalyzer and the basic alkyl characteristic of guaranteeing to be dissolved in basically hydrocarbon solvent.Specifically comprise representative compounds such as iso-butylene, 3-trimethyl silyl-2-methyl isophthalic acid-propylene, 2-methyl-1-butene alkene, 2-Methyl-1-pentene, 2-ethyl-1-amylene, 2-methyl isophthalic acid-hexene, 2-methyl isophthalic acid-heptene, 6-dimethylamino-2-methyl isophthalic acid-hexene, alpha-methyl styrene together with disubstituted olefin monomer.
But polycoordination monomer that can the copolymerization according to the present invention comprises one or more following monomer: C 3High alpha-olefin, vinylbenzene and substituting group alkyl substituted phenylethylene monomer, the C on aromatic ring more 6More senior substituted alpha-alkene, C 4More senior internal olefin, C 4More higher diene, and C 5More senior cycloolefin and diolefine.Preferred alpha-olefin comprises having 3 to 30 carbon atoms, and the alpha-olefin of preferred 3 to 20 carbon atoms has greater than 30 carbon atoms to the big monomer of 1-alkene up to about 100 carbon atoms and Geng Duo carbon atom but can use similarly.
Therefore preferred alpha-olefin comprises propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecylene, 4-methyl-1-pentene, 5-methyl isophthalic acid-nonene, 3-Methyl-1-pentene, 3,5,5-trimethylammonium-1-hexene and vinyl cyclohexane.Vinylbenzene and p-methylstyrene are preferred styrenic olefins.Preferred diolefine comprises ethylene copolymer, those that describe in EP and the EPDM rubber document particularly, disclosed content is special relevant therewith in the common pending application 08/545,973 (the October 20 nineteen ninety-five applying date), introduces as reference according to patent practice here.Example comprises straight chain acyclic dienes hydrocarbon, branching acyclic dienes hydrocarbon, monocycle alicyclic ring diolefine, many ring greases ring condenses and the alkene of bridged ring diolefine and cycloalkenyl group replacement.Preferred example is 1,4-hexadiene, Dicyclopentadiene (DCPD), 5-ethylidene-2-norbornene, vinyl cyclohexene and 5-vinyl-2-norbornylene.
C 6More senior substituted alpha-alkene comprises those alpha-olefins of the 13rd to 17 family's atom of the carbon atom bonding that contains at least one and substituted alpha-alkene.Example comprises allyl trimethyl silane, 4,4,4-three fluoro-1-butylene, methyl alkyl ether, methyl allyl sufide and DMAA.The alpha-olefin that use contains the functional group also within the scope of the present invention, when these alkene are introduced by the mode identical with its alpha-olefin analogue.Referring to " metalloscene catalyst in polyolefin block/graft reaction and borane reagent ", people such as T.C.Chung, the polymeric materials science engineering, the 73rd volume, p.463 (1995) and US's 5,153,282 shelters 'alpha '-olefin monomers.These monomers can prepare the multipolymer of the present invention of the derivatize subsequently that contains functional group and can be used as the big monomer of sense of grafting and block type polymerized segment.All documents are introduced as reference according to patent practice here.
Can comprise that cyclopentenes, norbornylene, alkyl replace norbornylene, tetrahydrobenzene, suberene and further be disclosed in background document and the patent documentation those according to the cycloolefin of copolymerization of the present invention, described patent documentation can be referring to WO 94/17113, common unsettled U.S.Ser.No.08/412,507 (the March 29 nineteen ninety-five applying date), and US 5,270,393 and 5,324,801.These documents are introduced as reference according to patent practice here.Polymerization process
The general method of preparation multipolymer of the present invention comprises at least a together with disubstituted olefin monomer and at least a ethylenically unsaturated monomer, optimal ethylene or propylene or other alpha-olefin, but with non-essential one or more other polycoordination monomers, the catalyst compound that is used for two (arylamino) the 4th family's catalyst compound of comprising of olefinic polymerization of a kind of bridging with activation contacts.This contact can be undertaken by activate catalyst composition is mixed under suitable insertion or polycoordination condition with polymerisable monomer.
Do not limiting under the condition of the present invention, it is believed that above-mentioned document and below explanation and embodiment in for example and the catalyst structure of describing play and make together with the easy polymeric effect of disubstituted olefin monomer, but mainly in the mode of not being obstructed near the metal-complexing center, and the space constraint by the catalyst compound ligand system and together with the mode polymerization of the space structure control of disubstituted olefin.The space together with the huge or space structure of disubstituted olefin and catalyst ligand system of inserting during inserting is bound plays the inhibition effect that enters the coordination center of catalyzer together with disubstituted olefin monomer following closely.Therefore insert subsequently together with disubstituted olefin usually after inserting ethene or other alpha-olefin.The monomer that is not subjected to insert previously together with disubstituted olefin of back suppresses like this, and can enter easily and insert.The multipolymer that obtains has and contains the described sequence segment that is essentially alternate cells.Obviously, multipolymer of the present invention has not obvious amount, the promptly essentially no diad together with disubstituted olefin that comprises homopolymerization or sequential polymerization, triad etc.
For copolymerization together with disubstituted olefin and ethene, be about 1000: 1 to 1: 1000 together with the preferred molar ratio of disubstituted olefin and ethene, more preferably from about 500: 1 to 1: 20, further more preferably 100: 1 to 1: 1.But any ratio that the inessential polycoordination monomer that is used for ethylene containing polymer can be consistent with required introducing ratio adds.For C 3-C 20Alpha-olefin/together with the disubstituted olefin monomer polymkeric substance, this ratio can be identical with the another kind of alpha-olefin of substituted ethylene.Polystyrene alkene, cycloolefin and any copolymerisable monomer be substituted ethylene similarly.For cyclic monoolefins, except preferably having some other copolymerisable monomers together with going back the disubstituted olefin monomer.Can get rid of cycloolefin/similarly together with the two performance of disubstituted olefin monomer and cyclic monoolefins monomer together with the disubstituted olefin monomer repeating unit.
Two (arylamino) the 4th family's catalyst compound of bridging of the present invention's (before activation) are prepared by other material of describing in known initial substance of describing in the above-mentioned document and the patent documentation according to present known synthetic technology.These compounds can be represented by following general formula: Wherein:
M is Zr, Hf or Ti, preferred Ti;
Q 1And Q 2Be phenyl independently, substituted-phenyl or its 15th family analogue, described substituting group is essentially alkyl, be preferably to be selected from and have 1 to 30 carbon atom, the alkyl of Siliciumatom or germanium atom, the group of silyl-alkyl or germyl-alkyl, or wherein one or more hydrogen atoms are by halogen group, amino, the phosphide group, alkoxyl group, the substituted hydrocarbon radical that aryloxy or any group that other contains Lewis acid or alkali functional group replace, silyl alkyl or germyl-alkyl, halogen group, or alkyl boride group, can be connected by covalent manner with two adjacent substituting groups wherein and to form the fused rings system thus;
Y is for having the bridged group of skeleton that forms 2-4 14-16 family element atom of 5-7 unit's metal ring (metallocycle) with the 4th group 4 transition metal and two amino ligands, and described atom is unsubstituted or is essentially as R by one or more 1And R 2Defined alkyl R ' replacement, wherein said R ' group can be alicyclic ring or aryl-condensed or hanging ring structure, comprises its 15th family analogue;
Z 1And Z 2Independently for being selected from hydride; Replace or do not replace C 1To C 30Alkyl; Alkoxide; The virtue oxide compound; Amide; Halogenide or phosphide; The single anion ligand of the 14th family's organic quasi-metal thing; And comprise that wherein two X can form part or any other two anion ligand of alkylidene group or ring metal substituted hydrocarbon radical together.
Preferred compound comprises having those group 4 metal compounds that are selected from following listed part:
Q 1Or Q 2Y Z
Ph-????????????????????????-(CH 2) 3-????????????????????-Cl
Figure A9880264400122
Two (arylamino) the 4th family's catalyst compound of bridging of the present invention can activate to be used for polymerization catalyzed by any way that is enough to carry out polycoordination.When a Z part is captured, another part Z can allow to insert unsaturated monomer or can capture similarly and replace when allowing to insert the Z of unsaturated monomer, can realize this activation.Traditional activator of metallocenes polymerization field is suitable, they generally include Lewis acid such as aluminium alkoxide compound and capture a Z part thus the transition metal central ion is turned to positively charged ion and provide contend with, the ionization negatively charged ion precursor compound of compatible non-coordination anion.
Alkylaluminoxane is particularly suitable as the catalyst activator of the metallic compound of the present invention that comprises the halogenide part.The aikyiaiurnirsoxan beta component that is used as catalyst activator is generally general formula, and (R " Al-O) nThe cyclic oligomer aluminum compound of expression, or general formula R " (R "-Al-O) nAlR " 2The linear oligomer aluminum compound of expression.In this aikyiaiurnirsoxan beta general formula, R " is C independently 1-C 10Alkyl, for example methyl, ethyl, propyl group, butyl or amyl group, " n " is 1 to about 50 integer.Most preferably R " is that methyl and " n " are at least 4.Aikyiaiurnirsoxan beta can be by prepared in various methods known in the art.For example, aluminum alkyls can be with the water treatment that is dissolved in the inert organic solvents, or can contact and generate aikyiaiurnirsoxan beta as being suspended in hydrated copper sulfate in the inert organic solvents with salt hydrate.Yet in common preparation method, aluminum alkyls and the reaction of limited amount water generate linear and ring-type aikyiaiurnirsoxan beta mixture.Methylaluminoxane is preferred.For further description, referring to US 4,665,208,4,952,540,5,041,584,5,091,352,5,206,199,5,204,419,4,874,734,4,924,018,4,908,463,4,968,827,5,329,032,5,248,801,5,235,081,5,157,137,5,103,031 and EP 0 561 476 A1, EP 0 279 586 B1, EP 0 516 476 A, EP 0 594 218 A1 and WO 94/10180, each document according to patent practice as with reference to introducing.
When activator was aikyiaiurnirsoxan beta, preferred transistion metal compound and activator mol ratio were 1: 2000 to 1: 10, more preferably from about 1: 500 to 1: 10, and further more preferably from about 1: 250 to 1: 10, most preferably from about 1: 100 to 1: 10.
Term be used for ionization negatively charged ion precursor compound " non-coordination anion " be meant not with described transition-metal cation coordination or only with described positively charged ion a little less than coordination be very easy to by neutral Lewis base metathetical negatively charged ion thus." compatible " non-coordination anion is not for being degraded to those negatively charged ion of neutral when the initial title complex that forms decomposes between two (arylamino) the 4th family's catalyst compound of bridging and the ionization negatively charged ion precursor compound.In addition, this negatively charged ion can not make anion substituent or fragment face south ion-transfer and the neutral by product that makes it form neutral four-coordination Metallocenic compound and be formed by this ion.Be used to implement non-coordination anion of the present invention and be such some negatively charged ion: they are compatible, the luxuriant positively charged ion of stable metal (are balance its+1 valency ionic charge), and keep it to allow between polymerization period by olefinic or acetylene series unsaturated monomer metathetical easiness.In addition, it is enough big to be used for its molecular dimension of negatively charged ion of the present invention, partly to suppress or to help to prevent that the metallocenes positively charged ion is present in Lewis base rather than the polymerisable monomer neutralization in the polymerization technique.This negatively charged ion has molecular dimension usually more than or equal to about 4 dusts.
Description about the ionic catalyst that is fit to polycoordination (comprise transition-metal cation and non-coordination anion those) appears at early stage works US 5,064,802,5,132,380,5,198,401,5,278,119,5,321,106,5,347,024,5,408,017, among WO92/00333 and the WO 93/14132.These documents disclose preferred manufacturing procedure, and wherein metallocenes is protonated by the negatively charged ion precursor, and the alkyl/hydride group is captured from transition metal like this, make it become positively charged ion and this non-coordination anion balancing charge of quilt.Similarly activating mechanism is fit to catalyzer of the present invention.
It also is known using the ionization ionic compound do not contain active proton but can generate active transition metallic cation and non-coordination anion.Referring to EP-A-0 426 637, EP-A-0 573403 and US 5,387,568.The reactive positively charged ion of non-Bronsted acid comprises ferrocene, silver, , triphenylcarbenium positively charged ion and triethylsilyl (Silylium), or basic metal or alkaline earth metal cation such as sodium, magnesium or lithium cation.Being fit to another kind of non-coordination anion precursor of the present invention is the salt hydrate that comprises basic metal or alkaline earth metal cation and above-mentioned non-coordination anion.Salt hydrate can pass through metallic cation-non-coordination anion salt and water prepared in reaction, for example commercially available or easy synthetic LiB (pfp) by hydrolysis 4, generate [LixH 2O] [B (pfp) 4], wherein (pfp) is pentafluorophenyl group or perfluorophenyl.These activation methods also are suitable.
Can form any metal of coordinate complex of water-fast (or other Bronsted or Lewis acid) degraded or metalloid can be used for or be contained in the negatively charged ion.Suitable metal includes but not limited to aluminium, gold, platinum etc.Suitable metalloid includes but not limited to boron, phosphorus, silicon etc.The non-coordination anion of describing in the document of top paragraph and its precursor are introduced as reference according to patent practice.
The other method of preparation ionic catalyst of the present invention adopts ionization negatively charged ion precursor, it when this precursor begins neutral lewis acid, but after carrying out ion reaction, form positively charged ion and negatively charged ion with group 4 metal compounds, for example three (pentafluorophenyl group) boron plays and captures the effect that alkyl, hydride or silyl part generate transition-metal cation and the non-coordination anion of stabilization, for similar approach, referring to EP-A-0 427 697 and EP-A-0 520 732.The ionic catalyst that is used for polycoordination also can pass through the metal center preparation of the negatively charged ion precursor oxidation transistion metal compound of containing metal oxide group and anionic group, referring to EP-A-0495 375.Similarly, the non-coordination anion of these document descriptions and its precursor are introduced as reference according to patent practice.
When the cationic moiety of the non-coordination precursor of ion is Bronsted acid such as proton or protonated Lewis base (not comprising water), or reducible Lewis acid such as ferrocene or silver-colored positively charged ion, or when basic metal or alkaline earth metal cation such as sodium, magnesium or lithium cation, transition metal and activator mol ratio can be any ratio, but preferred about 10: 1 to 1: 10, more preferably from about 5: 1 to 1: 5, further more preferably from about 2: 1 to 1: 2, most preferably from about 1.2: 1 to 1: 1.2, about 1: 1st of its ratio, most preferred.
When the Lewis acid that has Stable Carbon positively charged ion such as , triphenylcarbenium, hydrated alkali metal or alkaline-earth metal or its intensity to be enough to from water to discharge proton during as three (pentafluorophenyl group) boron, owing to be tending towards being independent of ethene and but multiple other polycoordination monomer carries out carbon cation polymerization together with disubstituted olefin, therefore only when reaction system do not contain the compound that can produce proton such as water substantially or when pure aforementioned proportion be preferred.If there are these compounds of trace, preferred transistion metal compound and activator mol ratio are 10: 1 to 1: 1, more preferably from about 5: 1 to 1: 1, and further more preferably from about 2: 1 to 1: 1, most preferably from about 1.2: 1 to 1: 1, ratio 1.05: 1st, most preferred.
When the Z part is not hydride, alkyl or silyl alkyl, as the muriate part, and in the time of can not capturing by the discontinuous ionization of ionization negatively charged ion precursor compound, these Z parts can transform by carrying out known alkylated reaction with organometallic compound such as lithium or alanate or alkylide, alkylaluminoxane, Grignard reagent etc.For being described in the similar approach that adds before the non-coordination anion precursor compound of activation or add the reaction of fashionable alkylaluminium cpd and dihalide substituted metal cyclopentadinyl compound, referring to EP-A-0 500 944, EP-A1-0 570 982 and EP-A1-0 612 768.Therefore, preferred catalytic activity the 4th group 4 transition metal catalyst component is transition-metal cation stable with the non-coordination anion of aforementioned arbitrary method deutero-and that contend with.
When use comprised the ionic catalyst of group-4 metal positively charged ion of the present invention and non-coordination anion, the total catalyst system also comprised one or more removing compounds usually.Those compounds that effectively remove the depolarization impurity from reaction environment intended comprising in the term " removing compound " that uses in the application and its claim.This term comprises that also proton scavengers is to suppress the competition carbon cation polymerization, referring to description and the explanation of WO 95/29940.Impurity can be with any polyreaction component, particularly be not intended to add with solvent, monomer and catalyzer raw material, and catalyst activity and stability are caused disadvantageous effect.Special when metallocenes positively charged ion-non-coordination anion when be catalyst system, these impurities cause catalytic activity reduction or even disappearance.These polarity impurities or catalyzer poison comprise water, oxygen, metal impurity etc.Before these components are added reactors, preferably take some steps, for example synthetic or prepare various components after or during carry out chemical treatment or carry out careful separation, but still normally in polymerization process itself use a small amount of removing compound.
Usually, the removing compound is the 13rd family's organometallic compound among organometallic compound such as US 5,153,157,5,241,025 and WO-A-91/09882, WO-A-94/03506, WO-A-93/14132 and the WO 95/07941.Its example comprises triethyl aluminum, triethylborane, triisobutyl aluminium, methylaluminoxane, isobutyl aluminium alkoxide and octyl aluminum.Those have the huge or C with metal or metalloid center covalent bonding 8-C 20The substituent removing compound of straight-chain alkyl is preferred for reducing to minimum with the unfavorable interaction of active catalyst.When aikyiaiurnirsoxan beta is used as activator, surpasses the effect that measures scavenger compounds of the metallocenes that exists, and do not need other removing compound.The scavenging agent amount of using right with respect to metallocenes positively charged ion-non-coordination anion can be reduced to during polyreaction effectively to be measured enhanced activity.
Catalyzer of the present invention can be loaded in and be used for gas phase, body, slurry phase polymerisation process on the carrier, or in other required method.The variety carrier method is that olefin copolymerization process, particularly aikyiaiurnirsoxan beta deactivated catalyst field are known, and arbitrary method is fit to the inventive method in wide region.For example, referring to US5,057,475 and 5,227,440.An example of carrier ionic catalyst is disclosed among the WO 94/03056.Special effective means is for being described in the method among common pending application U.S. serial number 08/474,948 (the June 7 nineteen ninety-five applying date) and the WO 96/04319.At US 5,001,205 and 5,229, described the luxuriant body or the slurry process of use aluminoxane catalyst activatory carrier bicyclic pentadiene group-4 metal of suitable ethylene-propylene rubber in 478, these methods also are fit to use catalyst system of the present invention.Can use inorganic oxide and polymer support according to the knowledge of this area.Referring to US5,422,325,5,427,991,5,498,582,5,466,649, common unsettled US patent application 08/265,532 and 08/265,533 (applying date all is 6/24/95) and international open WO 93/11172 and WO94/07928.Each above-mentioned document is introduced as reference here according to patent practice.
In the preferred embodiment of the inventive method, catalyst system is used for liquid phase (solution, slurry, suspension, body phase or its combination) middle and high press liquid or supercutical fluid phase or gas phase.These methods all can be used in single reactor, parallel reactor or tandem reactor.Liquid processes comprises that ethene contacts and make production multipolymer of the present invention thus of enough time of described monomer reaction with tying up to together with disubstituted olefin monomer and above-mentioned catalyst body in suitable diluents or the solvent.Aliphatic series and aromatic hydrocarbon solvent are suitable, and hexane and toluene are preferred.Body contacts with the slurry of liquid monomer by catalyzer usually with slurry process and carries out, and catalyst system can be loaded on the carrier.The similar use supported catalysts of gas phase process is also undertaken by any known way that is fit to prepare by polycoordination Alathon or multipolymer.Illustrative example can be at US4,543,399,4,588,790,5,028,670,5,382,638,5,352,749,5,436,304,5,453,471 and 5,463,999 and WO 95/07942 in find.Each document is introduced as reference according to the US patent practice.
Generally speaking, polymeric reaction temperature can be about 0 ℃ to about 250 ℃.The temperature of reaction condition optimization is 0 ℃ to 220 ℃, more preferably less than 200 ℃.Pressure can be about 1mm Hg to 2500 crust, and preferred 0.1 crust most preferably 1.0 to 500 clings to 1600 crust.When seeking lower molecular weight (M for example n≤ 10,000) during multipolymer, is adapted at temperature and is higher than about 0 ℃ and pressure and is lower than under 500 crust and carries out reaction method.US 5,278, and many boron activator of 119 also can be used for promoting to prepare the preparation of low-molecular weight copolymer of the present invention.
Those skilled in the art are apparent, catalyst compound of the present invention and component can with other catalyst system mix or with adopt one or more these type of catalyst systems connect or parallel reactor uses, preparation comprises the blend polymer of one or more multipolymers of the present invention or itself and has other polymkeric substance of the performance relevant with these blends (for example improving the wide polydispersity of polymer composition processibility and improvement polymer blend composition shock strength) and the blend of multipolymer thus.Industrial applicibility
Contain that the lower molecular weight alpha-olefin copolymer is known to can be used as the petroleum products additive and as the component of tackiness agent and encapsulant composition.In addition, because the feedstream that petroleum refinement generates can go out to comprise those products of low carbon number compound (2 to 4 carbon atoms) by fractionation separates from higher carbon number compound (more than 5 and 5), and owing to comprise alpha-olefin and iso-butylene than the low carbon number compound, the ability of therefore introducing iso-butylene contained in the feedstream and its analogue (1-butylene and 2-butylene) needs industrial.For example, referring to WO 93/24539, wherein be used as non-reactive diluent on the iso-butylene surface, unless the carbocation catalyzer adds with bicyclic pentadiene metallocenes coordination catalyst.
Multipolymer of the present invention (when particularly being essentially elastomerics) can be used in the lower molecular weight embodiment, as oily composition properties-correcting agent, and for example fuel or lubricating oil additive.
Other purposes is for using the ethene-alpha-olefin copolymer of the similar molecular weight with at least some ethene degree of crystallinity traditionally, as the linea low density and the ldpe copolymer field of ethene and 1-butylene, 1-hexene or 1-octene.Film and wrapping material can be by means commonly known in the art by these copolymer.In addition, available multipolymer of the present invention particularly is described as the surrogate of those multipolymers of plastomer as the higher alpha-olefin content multipolymer by the metalloscene catalyst preparation because of its elasticity, the preparation binder composition.As known in the art, these multipolymers can be used as base polymer, and it is configured for the binder composition of contact adhesive composition, hot-melt adhesive composition etc. with the tackifier resins, wax or the softening agent that add.For example, referring to common unsettled US application serial number 08/410,656 (applyings date 3/24/96) and 08/406,832 (applying date 3/20/95) and its international application WO 92/12212 of the same clan and WO 94/10256, each document is introduced as reference according to patent practice.
Embodiment
For explanation the present invention, provide following embodiment.These embodiment do not limit the present invention in any way, and only are used for illustration purpose.
Polymer performance passes through following determination of test method:
Except as otherwise noted, all molecular weight are weight-average molecular weight.Except as otherwise noted, molecular weight (weight-average molecular weight (M w) and number-average molecular weight (M n)) by gel permeation chromatography, with differential refraction rate detector being housed and measuring with Waters 150 gel permeation chromatographs of polystyrene standards calibration.With sample with three Shodex GPC AT-80 M/S pillars that are connected in series in THF (45 ℃) or 1,2, measure in the 4-trichlorobenzene (145 ℃) (solvability that depends on sample).This current techique is described in " the liquid chromatography III of polymkeric substance and associated materials " J.Cazes and writes, Marcel Decker, and 1981, among the p 207, introduce as reference according to patent practice here.Do not carry out pillar diffusion calibration; Yet, based on the data declaration M that can accept standard (for example National Bureau of Standards Polyethylene 1475) usually w/ M nCalculate by elution time) tolerance range be 0.1 unit.Use Expert Ease software to carry out data analysis available from WatersCorporation.
All are aggregated under the nitrogen atmosphere carries out with anhydrous solvent.Fill barytic pillar and make iso-butylene and 2-Methyl-1-pentene drying by steam or liquid are fed, for iso-butylene, with condensation in the body lotion of gas below being cooled to the boiling point of iso-butylene (b.p.～-10 ℃).Ethene is bought with 99.9% purity and is directly used.Solvent and scavenging agent (if use) are directly mixed in reactor under environmental stress, and before adding iso-butylene, it was mixed 5 minutes at least.Collect the iso-butylene of condensed fluid form.Under being lower than the temperature of its boiling point, add the iso-butylene of known volume in the reactor or adding to depress and force it to carry the compressed steel bottle to enter in the reactor.Ethene is added in the reactor under predetermined pressure with gas form.Add propylene similarly.Pressure listed in the table is pressure difference, is defined as to add preceding initial reactor pressure of ethene and the pressure difference between the ethene gauge pressure.Catalyzer the solvent of the external seldom volume of reactor (～2ml) in activation.
M nValue is with polystyrene equivalent thing record. 1H-and decoupling 13The C-NMR spectroscopic analysis is at CDCl 3Or toluene-d 8In use at ambient temperature intensity of field 250 MHz ( 13C-63 MHz) or at tetrachloroethane-d 2In 120 ℃ down with intensity of field 500MHz ( 13C-125MHz) (solubleness that depends on sample) carries out.The iso-butylene of introducing in the ethylene copolymer of embodiment 1 to 12 (mol%) is measured with following equation by methyl proton resonance integral and the contrast of methene proton resonance integral:
mol％IB＝100×(4A)/(6B+2A)
Wherein: A: the methyl resonance integral
B: methylene radical resonance integral
The high carbon number comonomer of introducing calculates with following equation.
Equation for the iso-butylene of introducing with propylene:
mol％IB＝[(C-5D)/(C+3D)]×100
The integration between the C:0.7 to 1.4ppm wherein
Integration between the D:1.4 to 1.7ppm
All at CDCl 3Middle mensuration
Equation for the iso-butylene of introducing with the 1-hexene:
mol％IB＝[(9E-3F)/(7E+3F)]×100
Wherein: E: the methyl resonance integral
F: methylene radical and methyne resonance integral embodiment
Catalyst precursor compound given below is used for embodiment.
Figure A9880264400211
Be reflected in the autoclave and between 20 to 30 ℃, carry out as monomer and solvent as catalyzer transfer solvent and iso-butylene with hexane.All monomers and solvent conventional drying box technology drying.Provide the representative processes of embodiment 1 as ethene/iso-butylene copolymerization.Embodiment 2-18 carries out with catalyzer, activator and comonomer dissimilar and amount similarly.These variations of embodiment 2-18 provide in table 1.Embodiment 1
The pure MAO of two parts of 240mg aliquot of weighing.1 aliquot is mixed in reactor under-30 ℃ with the liquid iso-butylene of 50ml.The MAO of another aliquot is mixed with 30mg A in being dissolved in the 1ml hexane.With activator and catalyst mix 5 minutes.Then this slurry is dropped in the reactor.Subsequently with the sealing of this reactor and be warmed to 21 ℃.Under this temperature, add ethene so that the rising 10psi when not having ethene of the pressure ratio in the reactor.This reaction mass was stirred 960 minutes.Then with the reactor release and add 1ml methyl alcohol.Be dissolved in polymkeric substance in the toluene and redeposition in methyl alcohol.At last with this product vacuum-drying.Output: 41.0g.By 1H-NMR (250Mhz) records this multipolymer and contains 39mol%IB.Embodiment 2-17
These embodiment carry out under the condition of embodiment 1, but with surrogate listed in the table 1.
Table 1
Operation Comonomer Catalyzer b Activator c Time Output The mol%IB that introduces M n M w/M n
Pressure (psi) a (mmol) (mmol) (min.) (g)
1 E，10 A，0.084 S，8.3 960 41.0 39 11,800 2.4
2 E，20 B，0.075 L，10.5 65 11.2 39 2100 2.6
3 E，20 C，0.066 S，6.6 120 14.0 33 7270 2.2
4 d E，20 C，0.066 S，6.6 120 20.6 38 4310 2.3
5 e E，20 C，0.066 S，6.6 120 0 --- --- ---
6 E，20 C，0.066 S，0.33 120 0 --- --- ---
7 E，20 C，0.066 S，1.65 120 1.1 22 8460 1.9
8 E，20 C，0.066 S，4.95 120 6.5 27 8640 2.4
9 E，20 C，0.066 S，13.2 120 17.5 38 4630 2.2
10 E，20 D，0.059 S，5.9 65 2.5 32 2520 2.1
11 E，20 E，0.054 S，5.4 65 1.1 24 4300 2.1
12 P，10 A，0.056 S，5.5 95 4.0 24 7940 1.9
13 P，10 B，0.075 L，10.5 65 1.9 18 1240 2.0
14 P，10 C，0.066 S，6.6 65 4.5 12 4700 2.1
15 P，10 D，0.059 S，5.9 65 4.2 8 3410 2.8
16 P，10 E，0.054 S，5.4 65 0.5 9 6290 2.3
17 H，1.35 B，0.075 L，5.3 73 0.9 44 550 1.3
Except as otherwise noted, all carry out with the 50ml iso-butylene under being reflected at 25 ℃.A) comonomer-E: ethene, P: propylene, H:1-hexene (with the gram number but not psi provide); B) A] 1, two (2,6-3,5-dimethylphenyl amino) the propane dimethyl titaniums of 3-; B] 1, two (2,6-3,5-dimethylphenyl amino) the propane titanium dichloride of 3-; C] 1, two (2,6-diethyl phenyl amino) the propane titanium dichloride of 3-; D] 1, two (2,6-diisopropyl phenyl amino) the propane titanium dichloride of 3-; E] 1, two (2,6-diisopropyl phenyl amino) the methylene radical dimethylsilane titanium dichloride of 3-; C) S] solid MAO; L] the 30wt% toluene solution of MAO; D) 60 ℃; ℃ e)-20

Claims (8)

1. one kind prepares the method that contains at least a olefin copolymer together with disubstituted olefin monomer, comprises being selected from ethene and C with at least a together with disubstituted olefin monomer and one or more 3-C 20The comonomer of alpha-olefin, but reach non-essential one or more other polycoordination monomers, contact with the catalyst system that comprises two (arylamino) the 4th family's catalyst components of a kind of bridging.
2. the process of claim 1 wherein the compound that two (arylamino) the 4th family's catalyst components of described bridging are represented derived from following general formula
Figure A9880264400021
Wherein:
M is Zr, Hf or Ti, preferred Ti;
Q 1And Q 2Be phenyl independently, substituted-phenyl or its 15th family analogue, described substituting group is essentially alkyl, be preferably to be selected from and have 1 to 30 carbon atom, the alkyl of Siliciumatom or germanium atom, the group of silyl-alkyl or germyl-alkyl, or wherein one or more hydrogen atoms are by halogen group, amino, the phosphide group, alkoxyl group, the substituted hydrocarbon radical that aryloxy or any group that other contains Lewis acid or alkali functional group replace, silyl alkyl or germyl-alkyl, halogen group, or alkyl boride group, can be connected by covalent manner with two adjacent substituting groups wherein and to form the fused rings system thus;
Y has a bridged group of skeleton that forms 3-4 14-16 family element atom of 6-7 unit metal ring with the 4th group 4 transition metal and two amino ligands, and described atom is unsubstituted or is essentially as R by one or more 1And R 2Defined alkyl R ' replacement, wherein said R ' group can be alicyclic ring or aryl-condensed or hanging ring structure, comprises its 15th family analogue;
Z 1And Z 2Independently for being selected from hydride; Replace or do not replace C 1To C 30Alkyl; Alkoxide; The virtue oxide compound; Amide; Halogenide or phosphide; The single anion ligand of the 14th family's organic quasi-metal thing; And comprise that wherein two X can form part or any other two anion ligand of alkylidene group or ring metal substituted hydrocarbon radical together.
3. claim 1 or 2 method, but wherein said other polycoordination monomer comprises at least a C of being selected from 3-C 30Alpha-olefin, C 6More senior substituted alpha-alkene, C 5More senior cycloolefin, and C 4The monomer of higher diene more.
4. claim 1 or 2 method, wherein said is iso-butylene or 2-Methyl-1-pentene together with disubstituted olefin monomer.
5. the method for claim 4, but wherein said other polycoordination monomer comprises at least a C of being selected from 3-C 30Alpha-olefin, C 6More senior substituted alpha-alkene, C 5-C 30Cycloolefin, or C 4-C 30The monomer of diolefine.
6. claim 1 or 2 method, the positively charged ion of two (arylamino) the 4th family's catalyst components of wherein said bridging for stablizing and contend with non-coordination anion.
7. claim 1 or 2 method, two (arylamino) the 4th family's catalyst components of wherein said bridging are activated by alkylaluminoxane.
8. a composition of olefin copolymer comprises C 3-C 20Alpha-olefin and together with the random basically multipolymer of disubstituted olefin.
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CN100389131C (en) 2008-05-21
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CA2278282C (en) 2007-07-31
DE69817542T2 (en) 2004-06-24
US6100354A (en) 2000-08-08
KR20000075567A (en) 2000-12-15
DE69817542D1 (en) 2003-10-02
KR100531533B1 (en) 2005-11-28
CA2278282A1 (en) 1998-08-27
EP0963384A1 (en) 1999-12-15
EP0963384B1 (en) 2003-08-27
ES2201445T3 (en) 2004-03-16

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